Precise measurement of hyperfine coupling in CH F based on nuclear spin conversion

A new method is proposed for the experimental determination of the hyperfine coupling in molecules. The method is based on the level-crossing effect in the spin isomer conversion in alternating electric fields. An experiment performed with the ¹³CH₃F molecules has revealed the strength of the off-diagonal in K () nuclear spin-spin coupling kHz, which is only by kHz larger than the theoretical value calculated on the basis of the molecular structure. Received 25 January 2000 and Received in final form 11 May 2000     

Experimental determination of spin-rotation and spin-spin magnetic interactions in by nuclear spin conversion

When a gas sample of ¹³CH₃F is prepared with a population of isomers (ortho and para forms) far from the equilibrium given by nuclear spin statistics, it relaxes towards this equilibrium with an exponential decay rate. This phenomenon called nuclear spin conversion is mainly governed by intramolecular spin-spin and spin-rotation interactions. In the quantum relaxation model [P.L. Chapovsky, Phys. Rev. A 43, 3624 (1991)], two pairs of ortho-para levels (J = 9, K = 3; J' = 11, K' = 1) and (J = 20, K = 3; J' = 21, K' = 1) are principally responsible for the conversion. The levels of the second pair are coupled by both spin-spin and spin-rotation interactions. The application of an electric field (up to 10 kV/cm) induces a crossing of the Stark components of this pair, which is observed for the first time. A specific experimental set-up based on an electric field of alternating triangular shape is used, which allows the determination of the strength of both interactions via the measurement of the spin conversion decay rates. This work yields the first experimental value for the electronic contribution to the spin-rotation interaction in ¹³CH₃F. Received 23 May 2002 / Received in final form 18 September 2002 Published online 21 January 2003 RID="a" ID="a"e-mail: Patrice.Cacciani@univ-lille1.fr     

Structure determination of mixed clusters by surface scattering

In this paper, we investigate the global structure of mixed clusters created by coexpansion. To determine the relative dopant sites within the mixed clusters, we take advantage of the strong dependence of the cluster/surface collision dynamics on the incident mixed cluster structure. Using both experiments and molecular dynamic simulations, we show that the coexpansion process leads to the most stable cluster structure for Ar _<880> Kr _<120> clusters. This structure corresponds to an annealed structure and can be characterized as a nearly homogeneous mixture throughout the cluster with a thin argon coating. Received 4 October 2000     

Resonance interaction between one excited and one ground state atom

The nature of the resonance interaction between two isotropic atoms in an excited configuration is reinvestigated. The currently accepted oscillatory form for the long-range retarded resonance interaction is shown to be a subtle artefact that arises due to too drastic approximations. Formulation of the resonance interaction energy problem in terms of the interacting system leads to a form that it is ∝ r ^-4 in the retarded limit. We also demonstrate that the resonance interaction energy at any finite temperature goes over to purely classical long-range asymptote. This manifestation of the correspondence principle is due to thermal excitation of the electromagnetic field. We finally discuss why the textbook result for the F?rster energy transfer between two atoms is incorrect for the same reasons. Received 31 January 2002 / Received in final form 25 July 2002 Published online 29 October 2002 RID="a" ID="a"e-mail: mtb110@rsphysse.anu.edu.au     

Zeeman effect of atomic uranium in the high lying odd levels measured by laser induced fluorescence spectroscopy

We measured Zeeman effect of atomic uranium spectra using laser induced fluorescence spectroscopy, and derived the J-value and g-factor of the second step levels. J-values and g-factors of high lying odd levels could be obtained. These data, especially the g-factors, have almost been unknown so far. We could verify our method which can be useful to measure J-values and g-factors of high lying levels of complex atoms like uranium. Received 27 July 1999 and Received in final form 30 November 1999     

Nuclear size correction to the hyperfine splitting in low- hydrogen-like atoms

The finite nuclear size effect on the hyperfine splitting of low-Z hydrogen-like atoms is studied in the external field approximation. A simple non-relativistic formula is proposed which expresses the nuclear size correction to the hyperfine splitting in terms of moments of the nuclear charge and magnetization distribution. The numerical results obtained via this formula are compared with corresponding results derived by means of the Zemach formula. A relativistic formula for the nuclear size correction to the hyperfine splitting is also derived. Received 18 March 2002 / Received in final form 14 November 2002 Published online 28 January 2003 RID="a" ID="a"e-mail: plunien@physik.tu-dresden.de     

Study of excitation transfer Li (3 D → 3 P ) occurring in optical collisions with rare gas atoms experimentally

By selective optical excitation of collision pairs and observation of the reemitted fluorescence information is obtained on the role of the molecular channels involved in inelelastic collisions. As an example case we have studied experimentally the Li( 3 D → 3 P) excitation transfer in Li(3D)X systems with X = Ne, Ar by means of the optical collision process Li (2 P ) + X + h ν→ LiX (3 D Λ) → Li (3 P , 3 D ) + X where LiX (3 D Λ) collision molecules dissociate into Li(3P, 3D) atoms following laser excitation h ν of Li (2 P ) + X pairs. For this purpose we measured the Li 3P/3D population ratio by the fluorescence from these levels as function of the laser detuning Δν from the Li(2P-3D) transition and the rare gas pressure, and determined from this the 3P/3D excitation ratio B (Δν) for single collision conditions. The experiments were performed using two step cw laser excitation of gaseous mixtures Li + X at temperatures around 600 K in the detuning range |Δν| ? 100 cm^-1. The B (Δν) profiles obtained display strong blue-red wing asymmetries both for Li ^* Ne and Li ^* Ar. This reflects different dissociation probabilities from the 3 D Σ or 3 D (Π,Δ) states that are initially prepared by blue wing or red wing excitation, respectively. The results are qualitatively discussed in terms of new ab initio potentials for the two systems. Received 23 February 2000 and Received in final form 5 July 2000     

Species selective evaporation during surface scattering of binary van der Waals clusters

We performed both experiments and molecular dynamics simulations for the scattering of mixed from a graphite surface under conditions where evaporation of thermalized small fragments is the main channel to evacuate the excess collision energy of the cluster impact. In spite of the expected thermal nature of the scattering process, we find average temperatures for the evaporating cluster particles that are considerably higher for krypton than for argon. We discuss the possible influence of the involved binding energies and the probable role of the incident cluster structure on these new results. Received: 28 January 1999     

Isotope-selective femtosecond wave packet dynamics: The rare molecule

For the first time, the femtosecond real-time vibrational dynamics of the rare ^41,41K₂ isotope, excited to the electronic state, could be selectively studied by means of time-resolved three photon ionization. A vibrational period of fs is determined. Superimposed, a beat structure with a period of 20 ps is observed. A detailed Fourier analysis reveals a strong band of three lines centered around 65.5 cm^-1. A significant perturbation of the wave packet caused by spin-orbit coupling of the A and the crossing state is found. This perturbation is the reason for the fast dephasing of the initially generated wave packet within about 10 ps. The spectrogram of the real-time data shows total revivals of the wave packet at 20 ps and 40 ps. Fractional revivals are found for times around 10 ps and 30 ps. Due to high intensity effects a remarkable slightly broadened line at 90 cm^-1 appears and can be assigned to the wave packet propagation generated in the dimer's ground state by impulsive stimulated Raman scattering. Revivals of this ground state wave packet are found at 17ps and 34ps. A comparison with other isotopes of K₂ is given. Received: 9 February 1998 / Revised: 15 May 1998 / Accepted: 2 June 1998     

Steric and energetic properties of the Cl-–C6H6–Arn heterocluster

The dynamics of heteroclusters containing argon, benzene and chlorine has been investigated using a recently proposed potential energy functional that takes into account both the electrostatic and the non-electrostatic contributions to the overall noncovalent interaction. Related steric and energetic properties are compared with those homologous cationic clusters.     

Finestructure, hyperfine structure and isotope shift of 4f 6s7s in Er I

The isotope shift (IS) and hyperfine structure (hfs) of nine levels (31720 to 38921 cm^-1) assigned to the configuration 4 f ¹² 6 s 7 s in neutral erbium have been determined experimentally using Doppler-reduced saturation absorption spectroscopy in a gas discharge. We performed a fine structure analysis in the SL-coupling scheme of the single configuration 4 f ¹² 6 s 7 s, confirming and extending the classification of even parity Er I levels. We discriminated the different hfs contributions of the 4f¹² core and the (6 s +7 s) outer electrons of the shell in a non-relativistic JJ-coupling approach and in the relativistic effective tensor operator formalism in SL-coupling. The relativistic one-electron parameters of the hfs for ¹⁶⁷Er were fitted to the experimental data by a least squares fit procedure: [0pt] a ⁰¹ _4f =-147(3) MHz, [0pt] a ¹⁰ _6s + a ¹⁰ _7s =-1840(30) MHz, [0pt] b ⁰² _4f =6560(80) MHz. The level dependencies of the isotope shift were evaluated based on crossed second order (CSO) effects. We obtained the following results for the CSO parameters for the isotope pairs ^170-168Er: d _6s7s =-740(30) MHz, z _4f = 0(5) MHz, ( g _3,6s ( f , 6 s )+ g _{3, 7s} ( f , 7 s ))= -24(15) MHz and for ^170-166Er: d _6s7s =-1500(50) MHz, z _4f =0(10) MHz, ( g _3,6s ( f ,6 s )+ g _3,7s ( f +7 s ))=-50(29) MHz. The resulting parameters for the hfs are compared with those known for other configurations of the Er atom and ion. Received 16 May 1999 and Received in final form 31 January 2000     

Quantum signatures in the dynamics of two dipole-dipole interacting soft dimers

The quantum covariances of physically transparent pairs of observables relative to two dimers hosted in a solid matrix are exactly investigated in the temporal domain. Both dimers possess fermionic and bosonic degrees of freedom and are dipolarly coupled. We find out and describe clear signatures traceable back to the presence and persistence of quantum coherence in the time evolution of the system. Manifestations of a competition between intramolecular and intermolecular energy migration mechanisms are brought to light. The experimental relevance of our results is briefly commented.     

Stimulated Raman spectroscopic study on intermolecular vibrations of size-selected benzonitrile clusters

Low frequency intermolecular vibrations of benzonitrile-(H₂O)_{n = 1 - 3}, -(CH₃OH)_{n = 1 - 3}, and -(CHCl₃)_{n = 1 - 3} clusters were observed by stimulated Raman - UV double resonance spectroscopy combined with fluorescence detection. The Raman active vibrations, which appear in the region from 5 to 50 cm^-1, exhibit characteristic frequency shifts depending on the cluster structure and on the cluster size. In benzonitrile-(H₂O)_{n = 1 - 3} and -(CH₃OH)_{n = 1 - 3}, the lowest frequency band showed a lower frequency shift with an increase of the number of solvent molecules. On the other hand, that of benzonitrile-(CHCl₃)_{n = 1 - 3} showed a shift to the higher frequency side. Their characteristic shifts are discussed based on the structure of the clusters. Received 28 April 2002 / Received in final form 30 May 2002 Published online 13 September 2002     

Decay reactions of rare gas cluster ions: Kinetic energy release distributions and binding energies

We have carried out measurements on metastable fragmentation of mass selected argon cluster ions which are produced by electron impact ionization of a neutral argon cluster beam. From the shape of the fragment ion peaks (MIKE scan technique) one can deduce information about the distribution of kinetic energy that is released in the decay reaction. In this study, for Ar ₅ ⁺ to Ar ₁₅ ⁺, it is Gaussian and thus we can calculate from the peak width the mean kinetic energy release 〈KER〉 of the corresponding decay reactions. Using finite heat bath theory we calculate from these data the binding energies of the decaying cluster ions. Received 20 November 2000     

Magnetic moments for lithium quartet S states

The fully correlated calculations of the Zeeman g_J factors for the first three quartet S states of lithium are presented, including relativistic and radiative corrections of orders α², α² m/M, and α³. The isotope shifts in g_J are predicted precisely for various isotopes of lithium. Received 4 December 2000 and Received in final form 26 September 2001     

Isotope effects in the metastable decay of Ne2 +

Neon dimer ions undergo spontaneous dissociation (metastable decay) several microseconds after formation by electron impact ionization of neon clusters. In this contribution we compare the kinetic energy release distribution (KERD) of the previously reported isotopomer ²⁰Ne₂ ⁺ with that of ²²Ne₂ ⁺. The heavy isotopomer shows the same two components in the KERD as the lighter ones. However, the high-energy component that is due to electronic pre-dissociation is reduced in intensity. The decrease is attributed to a reduced predissociation rate from the II(1/2u) state into I(3/2u).     

Cooling efficiency in collisions between Pd and He,Ne, Ar and Kr

The cooling of the metal cluster Pd₁₃ in an atmosphere of rare gas has been studied by means of computer simulation. By simulation, the average energy transfer in collisions between one cluster and one gas atom has been obtained. Emphasis has been placed on conditions when the temperatures of the colliding species are almost equal. All modes of motion, inclusive the translation, must be considered in order to obtain vanishing energy transfer at equilibrium. A simulation scheme is presented by which the energy transfer is zero to the cluster when the gas and the cluster temperatures are equal. At equilibrium the energy transfer does however not vanish for all impact parameters. In the collisions with Pd₁₃, the cluster is heated by collisions with a small impact parameter but equally cooled by collisions with a large impact parameter. Argon and krypton are found to cool Pd₁₃ equally efficiently while neon and helium are less efficient cooling agents. Received 28 September 2001 / Received in final form 8 August 2002 Published online 12 November 2002 RID="a" ID="a"e-mail: JanW@phc.gu.se     

Hyperthermal surface-collisions of water cluster cations

Size-selected, protonated water cluster cations (H₂O)_nH⁺, 4 n 32, are scattered at normal incidence from the surface of a diamond-coated silicon wafer at collision energies 0 E _coll 500 eV. The size distribution of collision-induced fragment-ions and the ion yield of scattered particles are analyzed, using a secondary time-of-flight mass spectrometer, as a function of the cluster size, n, and the collision energy, E _coll. Even at low impact energies only very small fragment-ions can be detected, with a maximum fragment size of 35% of the colliding parent cluster ions. For clusters consisting of more than 10 molecules, the protonated water dimer (H₂O)₂H⁺ becomes the predominant fragment-ion. The total charge survival yield obeys a nonlinear increase with cluster size; for the largest clusters investigated, more than 35% of the impacting ions survive the surface collision in the cationic charge state.     

Effective resolvent applied to interacting resonances

The wave operator theory of quantum dynamics is applied to characterize coupled metastable states. The theory extends to quasi bound states methods which are standard for dealing with bound levels. It is shown that interacting resonances can be investigated by means of small-dimensional effective Hamiltonians containing all the significant information of intrinsic properties which drive the various dynamical processes taking place. The study of the vibrational predissociation of I₂Ne, mediated by intramolecular energy redistribution, illustrates the power of the method. In addition to its accuracy to determine spectroscopic profiles and survival probabilities, it results more efficient than usual energy or time-domain numerical calculations. Received 25 January 2001 and Received in final form 11 May 2001     

Application of the stabilization method to interacting resonances

The stabilization method is applied to the case of interacting resonances in the photo-dissociation of van der Waals clusters composed by a rare gas atom bound to a dihalogen molecule. The study of an illustrative two-dimensional model consisting in a T-shaped NeI₂ molecule shows the adequacy of the method whenever the projection of the stabilization wave functions on the assumed prepared initial state is accounted for. The agreement of the fragmentation cross-sections with some previous results using the effective resolvent method and accurate close-coupling calculations is excellent. The method reveals its utility as a complementary tool since allows, through the analysis of the stabilization wave function in terms of zero-order levels, a precise characterization of the resonant states involved. Received 5 April 2002 / Received in final form 24 May 2002 Published online 19 July 2002